Chloro cyanobutanes



Patented Aug. 12, 1947 UNITED STATES PATENT OFFICE CHLORO CYANOBUTANES Joy G. Lichty, Stow, Ohio, assignor to Wingfoot Corporation, Akron, Ohio, a corporation N Drawing. Application May 7, 1943, Serial No. 486,113

3 Claims. (Cl. 260-464) This invention relates to certain chloro compounds and their preparation and, more particularly, to chloro cyanobutanes and a method of obtaining the same.

The pyrolysis of 2-cyano-2-acetoxybutane results in the production of three unsaturated compounds; namely, l-methyl crotononitrile, cis and trans forms, and l-ethyl acrylonitrile. The course of the pyrolysis may be indicated as fol- Example 1 From the pyrolizate resulting from the pyrolysis of 2-cyano-2-acetoxybutane was taken 242 grams of a fraction boiling at 11'7-l38 C. This product consisted in the main of the cis and trans 1-methyl crotononitriles, but undoubtedly contained some l-ethyl acrylonitrile.

Chlorine was bubbled into the pyrolizate fraction while grams.

cooling until the increase in weight was 179 The theoretical increase in weight for the addition of one mol of chlorine at a temperature below 45 C. to one mol of the methyl crotononitrile is 212. grams. uct was then distilled and the following frac- The addition prodtions obtained:

Fraction Boiling point Wt., g. :55a Density Ref. index 74 0.]28 mm 24.6 74-82 O./28 mm 205. 6 54 D15 l. 161 N D=1. 4508 82 O./28 mm172 C./16 mm 25.2 172176 C./l7 mm 83. 0 22 Dus=1. 251 Nn=l. 4964 Fraction 2 is the l-methyl-l,2-dichlorbutyronitrile or 2-3 dichloro 2-cyanobutane While fraction 4 probably is the dimer of this compound.

Example 2 The method was also applied to the chlorination of l-ethyl acrylonitrile. Here 162 grams of l-ethyl acrylonitrile was chlorinated at a temperature of C. or less until the increase in weight was slightly more than the theoretical. 40 Distillation gave the following fractions:

Fraction Boiling point Wt., g g gg Density Rel. index 1 82 O./28 mm 9.1 2 82-86 G. 28 mm 195. 5 64 D15 =l. 192 N =L 4539 3 86l20 ./28 mm 31.6 4 180190 O./28 mm 38.0 12 D =L 273 ND27=L 5003 chloro 2-cyanobutane. The reaction is indicated In this instance, fraction 2 is l-(chloromethyhl-chlorbutyronitrile or 1,2-dichloro 2-cyanobutane and fraction 4 its dimer.

In carrying out the process the 2-cyanobutene,

Of course,

less chlorine may be passed in with consequent reduction in yield, but preferably an excess will be employed to insure as far as possible that all of the organic ingredient is utilized. The products may be separated by fractional distillation or other suitable means.

The dichloro 2-cyanobutanes are believed to be new compounds. The class includes the 2-chloro 2-cyanobutanes containing an additional chlorine radical, particularly those in which the chlorine radical is in one of the positions adjacent to the 2-position, e. g., 2;,3-dichloro 2-cyanobutane and 1,2-dichloro 2-cyanobutane.

The chloro cyanobutanes are useful as intermediates in the preparation of polymerizable organic compounds, such as those obtainable by pyrolysis. They may also be useful as fumigants or insecticides.

While there have been described above certain preferred embodiments of the invention, it will be apparent to those skilled in the art that var-- ious modifications and changes may be made therein withoutdeparting from the spirit of the invention or the scope of the appended claims.

I claim:

1. The 2-chloro Z-cyanobutanes containing an additional chlorine radical in one of the positions adjacent to the Z-position.

2. 2,3-dichloro 2-cyanobutane.

3. 1,2-dichloro 2-cyanobutane.

JOY G. LICHTY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Pieroh Oct. 3, 1939 FOREIGN PATENTS Country Date Australia Aug. 13,1942

. OTHER REFERENCES Number Number 

